TY - JOUR
T1 - Insights into the Structure of Cyclohexane from Femtosecond Degenerate Four-Wave Mixing Spectroscopy and Ab Initio Calculations
AU - Riehn, Christoph
AU - Matylitsky, Victor V.
AU - Jarzȩba, Wlłodzimierz
AU - Brutschy, Bernd
AU - Tarakeshwar, P.
AU - Kim, Kwang S.
PY - 2003/12/31
Y1 - 2003/12/31
N2 - In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B0 with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order Moøller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A1g modes, a justification of which is provided by an analysis of these modes.
AB - In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B0 with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order Moøller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A1g modes, a justification of which is provided by an analysis of these modes.
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U2 - 10.1021/ja036615o
DO - 10.1021/ja036615o
M3 - Article
C2 - 14692789
AN - SCOPUS:0347064288
SN - 0002-7863
VL - 125
SP - 16455
EP - 16462
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 52
ER -